EP0134752A1 - Layered material and its use - Google Patents

Abstract

Coated material from a support on which a radiation-sensitive from a homo- or copolymer with at least 5 mol .-%, based on the polymer, structural units of the formula I <IMAGE> wherein R is a divalent aliphatic radical which is substituted by heteroatoms, aromatic, heterocyclic or cycloaliphatic groups can be interrupted, a cycloaliphatic, heterocyclic or araliphatic radical, an aromatic radical in which two aryl nuclei are linked via an aliphatic group, or one by at least one alkyl group, cycloalkyl group, alkoxy group, alkoxyalkyl group, alkylthio group, alkylthioalkyl group, hydroxyalkyl group, hydroxyalkoxy group Hydroxyalkylthio group, aralkyl group or two adjacent C atoms of the aromatic radical is an aromatic radical substituted by an alkylene group, R 'independently has the same meaning as R and q represents 0 or 1, where R as an aromatic radical is not by alkylene and not by those previously rest mentioned e is substituted when q = 0 is applied. The layer can be crosslinked directly by exposure to radiation. The material is suitable, for example, for the production of protective films and relief images.

Description

The present invention relates to a support coated with a radiation-sensitive polymer, the polymer containing benzophenonetetracarboximide units, and to the use of this material for the photographic production of relief structures and protective films.

Photographic imaging processes using radiation-sensitive polymers to produce relief images have become very important for the production of components in electronics and semiconductor technology. Depending on the intended use, certain properties are required of such photopolymers and various types of polymers have become known for this purpose. The photosensitivity of such polymers is relatively low, which requires the addition of photoinitiators or sensitizers in order to achieve economical exposure times. A disadvantage of such additives is that they can reduce the mechanical and physical properties.

For certain applications, high temperature resistance of the structures produced or photochemically produced protective coatings are also desired. Polyimides are particularly suitable for this.

Because of their insolubility, soluble precursors must be assumed, which are only converted into polyimides by thermal aftertreatment after photopolymerization. A direct photocrosslinking of polyimides has so far not been disclosed.

From the D _E -A-30 07 445 polyamides and polyesters with Benzophenontetracarbonsäureimideinheiten are known. The physical-mechanical properties of fibers or films made from this material can be improved by exposure. Nothing is mentioned about the production of protective coatings or photographic imaging processes.

worin R ein zweiwertiger unsubstituierter oder substituierter aliphatischer Rest, der durch Heteroatome, aromatische, heterocyclische oder cycloaliphatische Gruppen unterbrochen sein kann, ein unsubcycloaliphatischer stituierter oder substituierter, heterocyclischer,/oder araliphatischer Rest,ein aromatischer Rest, bei dem zwei Arylkerne über eine aliphatische Gruppe verknüpft sind, oder ein durch mindestens eine Alkylgruppe, Cycloalkylgruppe, Alkoxyalkylgruppe, Alkoxygruppe, Alkylthiogruppe, Alkylthioalkylgruppe, Hydroxyalkylgruppe, Hydroxyalkoxygruppe, Hydroxyalkylthiogruppe, Aralkylgruppe oder zwei benachbarte C-Atome des aromatischen Restes durch eine Alkylengruppe substituierter aromatischer Rest ist, R' unabhängig die gleiche Bedeutung wie R hat und q für 0 oder 1 steht, wobei R als aromatischer Rest nicht durch Alkylen oder nicht in beiden Orthostellungen zum N-Atom durch die zuvor genannten Reste substituiert ist, wenn q = 0 ist.The present invention relates to a coated material made of a support onto which a radiation-sensitive polymer is applied as a layer, which is characterized in that the polymer is a homo- or copolymer with at least 5 mol.Z, based on the polymer, structural units of the formula I is

wherein R is a divalent unsubstituted or substituted aliphatic radical which can be interrupted by heteroatoms, aromatic, heterocyclic or cycloaliphatic groups, an unsubcycloaliphatic substituted or substituted, heterocyclic, / or araliphatic radical, an aromatic radical in which two aryl nuclei are linked via an aliphatic group are, or an aromatic radical substituted by at least one alkyl group, cycloalkyl group, alkoxyalkyl group, alkoxy group, alkylthio group, alkylthioalkyl group, hydroxyalkyl group, hydroxyalkoxy group, hydroxyalkylthio group, aralkyl group or two adjacent C atoms of the aromatic radical by an alkylene group, R 'independently has the same meaning as R has and q represents 0 or 1, where R as aromatic radical is not substituted by alkylene or not in both ortho positions to the N atom by the aforementioned radicals if q = 0.

The amount of structural elements of the formula I depends essentially on the desired photosensitivity of the homo- or copolymers and on their structure. The amount can be 5 to 100 mol%, preferably 20 to 100 mol%, particularly 40 to 100 mol% and in particular 50 to 100 mol%, based on the polymer. Homopolymers and copolymers with 80-100 mol% of structural elements of the formula I are very particularly preferred.

In the case of homopolymers or copolymers with structural elements of the formula I in which R and R 'are an aliphatic or cycloaliphatic radical, the amount of these structural elements is preferably at least 50 mol%, especially if the homopolymers and copolymers are polyamides and polyesters acts.

Beispiele für aliphatische Reste sind: Methylen, Aethylen, 1,2-oder 1,3-Propylen, 2,2-Dimethyl-1,3-propylen, 1,2-, 1,3- oder 1,4-Butylen, 1,3- oder 1,5-Pentylen, Hexylene, Heptylene, Octylene, Decylene, Dodecylene, Tetradecylene, Hexadecylene, Octadecylene, Eicosylene, 2,4,4-Trimethylhexylen, 1,10-Dialkyldecylen, wobei das Alkyl bevorzugt 1- bis 6 C-Atome aufweist, substituierte 1,11-Undecylene, wie sie z.B. in der EP-B-0 O11 559 beschrieben sind, Jeffamine wie z.B.

mit p = 1 bis 100 oder -(CH₂)̵₃(̵0(CH₂)₄)̵O(̵CH₂)̵₃ mit ^p = 1-100, Dimeth^ylenc^yclohexan, Xylylen und Diäthylenbenzol. Besonders bevorzugt sind R bzw. R' längerkettiges, verzweigtes Alkylen mit z.B. 8 bis 30 C-Atomen.R or R 'in formula I as a divalent aliphatic radical preferably contains 2 to 30, particularly 6 to 30 and in particular 6 to 20 C atoms. In a preferred subgroup, R or R 'is linear or branched alkylene, which can be interrupted by oxygen atoms, S, SO, SO ₂ , NH, NR ^a , ^⊕ NR ^a ₂ G ^⊖ , cyclohexylene, naphthylene, phenylene or hydantoin ^residues . R can be, for example, alkyl having 1 to 12 carbon atoms or cycloalkyl having 5 or 6 ring carbon atoms, phenyl or benzyl. G ⊖ means an anion of a protonic acid, for example halide, sulfate, phosphate. In a preferred embodiment, R or R ^{1 are} linear or branched alkylene having 6 to 30 C atoms, - (CH ₂ ) _m -R ¹ - (CH ₂ ) _n -, wherein R ^{1 is} phenylene, naphthylene, cyclopentylene or cyclohexylene and m and n are independently the number 1, 2 or 3, -R ² (̵O ^R ) ̵-OR ² -, in which R ^{2 is} ethylene, 1,2-propylene, 1,3-propylene or 2-methyl1-1, 3-propylene and R3 are ethylene, 1,2-propylene, 1,2-butylene, 1,3-propylene or 1,4-butylene and p is a number from 1 to 100, or

Examples of aliphatic radicals are: methylene, ethylene, 1,2- or 1,3-propylene, 2,2-dimethyl-1,3-propylene, 1,2-, 1,3- or 1,4-butylene, 1 , 3- or 1,5-pentylene, hexylene, heptylene, octylene, decylene, dodecylene, tetradecylene, hexadecylene, octadecylene, eicosylene, 2,4,4-trimethylhexylene, 1,10-dialkyldecylene, the alkyl preferably 1-6 Has carbon atoms, substituted 1,11-undecylenes, as described, for example, in EP-B-0 O11 559, Jeffamines, for example

with p = 1 to 100 or - (CH ₂ ) ̵ ₃ (̵0 (CH ₂ ) ₄ ) ̵O (̵CH ₂ ) ̵ ₃ with ^p = 1-100, dimeth ^y lenc ^y clohexane, xylylene and diethylene benzene. R or R 'are particularly preferred long-chain, branched alkylene having, for example, 8 to 30 carbon atoms.

bedeuten, worin R¹⁶ und R¹⁷ C₁-C₆-Alkyl, besonders Methyl, oder Phenyl sind, _R ²⁰ Cycloalkylen wie z.B. Cyclohexylen und besonders C₁-C_12' insbesondere C₁-C₆-Alkylen, z.B. 1,3-Propylen oder 1,4-Butylen, ist und x für eine rationale Zahl von mindestens 1, z.B. 1 bis 100, bevorzugt 1 bis 10 steht. Solche Diamine mit diesem Rest sind in der US-PS 3 435 002 und US-PS 4 030 948 beschrieben.R or R 'in formula I can also be a polysiloxane radical of the formula as an aliphatic radical

mean in which R ¹⁶ and R ^{17 are} C ₁ -C ₆ alkyl, especially methyl, or phenyl, _R ²⁰ cycloalkylene such as cyclohexylene and especially C ₁ -C _{12 ',} in particular C ₁ -C ₆ alkylene, eg 1.3 -Propylene or 1,4-butylene, and x represents a rational number of at least 1, for example 1 to 100, preferably 1 to 10. Such diamines with this residue are described in U.S. Patent 3,435,002 and U.S. Patent 4,030,948.

worin R^b Alkylen mit 1 bis 12, bevorzugt 1 bis 4 C-Atomen oder -(CH₂CHO)_aCH₂CH₂ ist, worin Rc ein Wasserstoffatom oder Methyl R^c und a ganze Zahlen von 1-20 bedeuten.The aliphatic radicals interrupted by heterocyclic radicals can be, for example, those which are derived from N, N'-aminoalkylated hydantoins or benzimidazoles. Examples are N, N '- (y-aminepropyl) -5,5-dimethyl-hydantoin or -benzimidazolone and those of the formula

in which R ^{b is} alkylene having 1 to 12, preferably 1 to 4, carbon atoms or - (CH ₂ CHO) _a CH ₂ CH ₂ , in which Rc is a hydrogen atom or methyl R ^c and a is an integer from 1-20.

Suitable substituents for the aliphatic radicals are e.g. Hydroxyl, halide such as F or Cl or alkoxy with 1 to 6 carbon atoms.

Heterocyclic diamine residues are preferably derived from N-heterocyclic diamines, e.g. of pyrrolidine, indole, piperidine, pyridine, pyrrole, the N atom of which is alkylated, e.g. can be methylated. An example is N-methyl-4-amino-5-aminomethylpiperidine.

oder

worin q 0 oder 1 ist, die R⁴ unabhängig Wasserstoff oder Alkyl mit 1 bis 6 C-Atomen bedeuten und X für eine direkte Bindung, ₀, S, SO₂, Alkylen mit 1 bis 3 C-Atomen oder Alkyliden mit 2 bis 6 C-Atomen steht. R⁴ ist bevorzugt Aethyl und Methyl, X bevorzugt Methylen und das Alkyliden enthält bevorzugt 2 oder 3 C-Atome, wie Aethyliden und 1,1- oder 2,2-Propyliden.R or R 'in formula I in their meaning as a divalent cycloaliphatic radical preferably contains 5 to 8 ring C atoms and are particularly unsubstituted or mononuclear or dinuclear cycloalkylene substituted by alkyl which preferably contains 1 to 4 C atoms 5 to 7 ring carbon atoms. In a preferred embodiment, R and R 'as cycloaliphatic radical are those of the formulas

or

in which q is 0 or 1, R ^{4 is} independently hydrogen or alkyl having 1 to 6 carbon atoms and X is a direct bond, ₀ , S, SO ₂ , alkylene with 1 to 3 carbon atoms or alkylidene with 2 to 6 carbon atoms. R ⁴ is preferably ethyl and methyl, X is preferably methylene and the alkylidene preferably contains 2 or 3 carbon atoms, such as ethylidene and 1,1- or 2,2-propylidene.

Examples of R or R 'as cycloalkylene are: 1,2- or 1,3-cyclopentylene, 1,2-, 1,3- or 1,4-cyclohexylene, cycloheptylene, cyclooctylene, methylcyclopentylene; Methyl or dimethylcyclohexylene, 3- or 4-methylcyclohex-l-yl, 5-methyl-3-methylenecyclohex-l-yl, 3,3'- or 4,4'-bis-cyclohexylene, 3,3'- dimethyl-4,4'-biscyclohexylen, 4,4'-Biscyclohexylenäther or sulfone, or methane or -2,2-propane, and the remains of bis-aminomethy1 ₇ tricyclodecane, bis-aminomethylnorbornan and menthanediamine.

R and R 'are particularly preferred as cycloaliphatic radical 1,4- or 1,3-cyclohexylene, 2,2,6-trimethyl-6-methylene-cyclohex-4-yl, methylenebis (cyclohex-4-yl) or methylenebis (3-methylcyclohex-4-yl).

R or R 'as an araliphatic radical preferably contain 7 to 30 carbon atoms. If the aromatic group of the araliphatic radical is bonded to the N atoms in the radical of the formula I, which is preferred, these aromatic groups are preferably substituted as R or R 'as aromatic radical, including the preferences.

worin die R⁴ unabhängig voneinander ein Wasserstoffatom oder besonders Alkyl mit 1-6 C-Atomen und r ganze Zahlen von 1-20 bedeuten.The araliphatic radical preferably contains 7 to 30, especially 8 to 22, carbon atoms. The aromatic radical in the araliphatic radical is preferably a phenyl radical. In their meaning as an araliphatic radical, R or R 'are particularly unsubstituted or aralkylene which is substituted on the aryl by alkyl, the alkylene radical being linear or branched. In a preferred embodiment, the araliphatic radical corresponds to the formula

wherein the R ⁴ independently of one another represent a hydrogen atom or, in particular, alkyl having 1-6 C atoms and r are integers from 1-20.

The free bond can be in the o-position, m-position and especially in the p-position to the C _r H _2r group and one or both R ⁴ are preferably bonded in the o-position to the free bond.

Examples of R or R 'as araliphatic radical are: m- or p-benzylene, 3-methyl-p-benzylene, 3-ethyl-p-benzylene, 3,5-dimethyl-p-benzylene, 3,5-diethyl -p-benzylene, 3-methyl-5-ethyl-p-benzylene, p-phenylene propylene, 3-methyl-p-phenylene propylene, p-phenylene butylene, 3-ethyl-p-phenylene pentylene and in particular longer-chain phenylene alkylene radicals, for example EP-A-0 069 062 describes: 6- (p-phenylene) -6-methylhept-2-yl, 6- (3'-methyl-p-phenylene) -6-methylhept-2-yl, 6 - (3'-Ethyl-p-phenylene) -6-methylhept-2-yl, 6- (3 ', 5'-dimethyl-p-phenylene) -6-methylhept-2-yl, 11- (p-phenylene ) -2,11-dimethyl-dodec-1-yl, 13- (p-phenylene) -2,12-dimethyltetradec-3-yl.

worin die freien Bindungen in p-, m- und besonders o-Stellung zur Q-Gruppe gebunden sind und Q C₁-C₁₂-, besonders C₁-C₆-Alkylen ist, das durch 0 oder S unterbrochen sein kann. Beispiele für Q sind _Aethylen, 1,2- oder 1,3-Propylen, Butylen, -CH₂-0-CH₂, -CH₂-S-CH₂-und -CH₂CH₂-O-CH₂CH₂-.R or R 'can also be an aromatic radical in which two aryl nuclei, especially phenyl, are linked via an aliphatic group. This rest preferably corresponds to the formula

in which the free bonds in the p-, m- and especially o-position are bonded to the Q group and QC ₁ -C ₁₂ -, especially C ₁ -C ₆ -alkylene, which can be interrupted by 0 or S. Examples of Q, _A, ethylene, 1,2- or 1,3-propylene, butylene, -CH ₂ -0-CH _2, -CH ₂ -S-CH ₂ and -CH ₂ CH ₂ -O-CH ₂ CH ₂ -.

Among the homopolymers and copolymers, those with structural elements of the formula I in which R or R 'are substituted aromatic radicals are particularly preferred. The substituent on the aromatic radical preferably contains 1 to 20, especially 1-12 and in particular 1-6 C atoms. In particular, the substituent is C or C ₆ cycloalkyl, linear or branched alkyl, alkoxy, alkoxyalkyl, alkylthio, alkylthioalkyl, hydroxyalkyl, hydroxyalkoxy or hydroxyalkylthio having 1 to 6 C atoms, benzyl, trimethylene or tetramethylene. Alkoxymethyl is preferred as alkoxyalkyl and methoxy as alkoxy. Examples of the substituent are: methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, pentyl, hexyl, octyl, dodecyl, tetradecyl, eicosyl, methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, methoxymethyl, methoxyethyl, Aethoxymethyl, propoxymethyl, butoxymethyl, benzyl, methylbenzyl, phenylethyl, methylthio, ethylthio, hydroxyethyl, methylthioethyl and hydroxyethylthio. Preferred radicals are methoxymethyl, ethoxymethyl, methyl, ethyl, n-propyl, i-propyl, trimethylene and tetramethylene, cyclopentyl and cyclohexyl. Methyl, ethyl and i-propyl are particularly preferred. The substituted aromatic radical can be mononuclear or multinuclear, especially dinuclear, radicals. Mononuclear radicals can contain up to 4, preferably 2, especially 1, substituents and binuclear radicals can contain up to 4, preferably 1 or 2, substituents in each nucleus. It was found that the photosensitivity of homo- or copolymers is particularly high if one or two substituents are bonded ortho to the N atom. The substitution in ortho position is therefore preferred. The aromatic radical is preferably bound to the N atom in the meta or para position.

R or R 'can be 7 to 30, especially 7 to 20, as aromatic residue Contain carbon atoms. The aromatic radical is preferably a hydrocarbon radical or pyridine radical which is substituted as previously defined.

oder

worin R4 im Falle der Monosubstitution Alkyl mit 1 bis 6 C-Atomen und die anderen R⁴ Wasserstoff sind, und im Falle der Di-, Tri- oder Tetrasubsti_tution zwei R⁴ Alkyl mit 1 bis 6 C-Atomen und die anderen R⁴ ein Wasserstoffatom oder Alkyl mit 1 bis 6 C-Atomen sind oder im Falle der Di-, Tri- oder Tetrasubstitution zwei vicinale R⁴ im Phenylring für Trimethylen oder Tetramethylen und die anderen _R ⁴ für ein Wasserstoffatom oder Alkyl mit 1 bis 6 C-Atomen stehen, Y für 0, S, NH, CO oder CH₂ steht, R⁵ ein Wasserstoffatom oder Alkyl mit 1 bis 5 C-Atomen und R⁶ Alkyl mit 1 bis 5 C-Atomen darstellt, und Z eine direkte Bindung, 0, S, SO, SO₂, CO, 0 0 CO, CNR , NR, CONH, NH, R SiR , R7^OSiOR⁸,A preferred subgroup are such aromatic radicals of the formulas

or

wherein R4 is in the case of mono-substitution is alkyl having 1 to 6 carbon atoms and the other R ⁴ is hydrogen, and in the case of di-, tri- or Tetrasubsti _t ution two R ⁴ is alkyl having 1 to 6 carbon atoms and the other R ^{4 are} a hydrogen atom or alkyl having 1 to 6 carbon atoms or, in the case of di, tri or tetra substitution, two vicinals R ⁴ in the phenyl ring represents trimethylene or tetramethylene and the other _R ^{4 represent} a hydrogen atom or alkyl having 1 to 6 carbon atoms, Y represents 0, S, NH, CO or CH ₂ , R ^{5 represents} a hydrogen atom or alkyl having 1 to 6 carbon atoms 5 carbon atoms and R ⁶ alkyl having 1 to 5 carbon atoms, and Z is a direct bond, 0, S, SO, SO ₂ , CO, 0 0 CO, CNR, NR, CONH, NH, R SiR, R7 ^O SiOR ⁸ ,

Alkylen mit 1 bis 6 C-Atomen, das durch -0- oder -S- unterbrochen sein kann, Alkenylen oder Alkyliden mit 2 bis 6 C-Atomen, Phenylen oder Phenyldioxyl bedeutet, worin R⁷ und R⁸ unabhängig voneinander Alkyl mit 1 bis 6 C-Atomen oder Phenyl bedeuten und j für 1-10, besonders 1-3 steht. Z kann weiter der Formel

entsprechen worin G für S und besonders für 0 steht, f 0 oder besonders 1, g 1-6 und h 1 bis 50, besonders 1 bis 10 bedeuten, und R¹⁶ und _R ¹⁷ die zuvor angegebene Bedeutung haben,sowie einen Rest der Formel

entsprechen worin K für -

mit R²⁵ gleich H, C₁-C₆-Alkyl oder Phenyl steht. R⁵ und R⁶ sind bevorzugt Methyl, Y steht bevorzugt für -CH₂- oder -0- und Z bevorzugt für eine direkte Bindung, -0-, -CH₂- oder Alkyliden mit 2 bis 4 C-Atomen. R⁷ und R⁸ stehen besonders für Methyl, Aethyl und Phenyl. Das Alkylen enthält bevorzugt 2 bis 4 C-Atome und ist besonders Aethylen. Alkenylen ist besonders Aethenylen.

Alkylene with 1 to 6 carbon atoms, which can be interrupted by -0- or -S-, alkenylene or alkylidene with 2 to 6 carbon atoms, phenylene or phenyldioxyl, where R ⁷ and R ⁸ independently of one another are alkyl with 1 to 6 is carbon atoms or phenyl and j is 1-10, especially 1-3. Z can continue the formula

correspond in which G represents S and especially 0, f represents 0 or especially 1, g 1-6 and h 1 to 50, particularly 1 to 10, and R ¹⁶ and _R ^{17 have} the meaning given above, and a radical of the formula

where K for -

where R ²⁵ is H, C ₁ -C ₆ alkyl or phenyl. R ⁵ and R ⁶ are preferably methyl, Y preferably represents -CH ₂ - or -0- and Z preferably represents a direct bond, -0-, -CH ₂ - or alkylidene having 2 to 4 carbon atoms. R ⁷ and R ⁸ stand especially for methyl, ethyl and phenyl. The alkylene preferably contains 2 to 4 carbon atoms and is especially ethylene. Alkenylene is especially ethenylene.

A preferred subgroup are tolylene residues, residues of 0.0'-substituted diaminodiphenylenes, diaminodiphenylmethanes and diaminodiphenyl ether.

oder

worin Z eine direkte Bindung, 0 und besonders CH₂ bedeutet und _R ⁹ ein Wasserstoffatom, Methyl, Aethyl oder Isopropyl darstellt.A particularly preferred group are such aromatic radicals of the formulas

or

wherein Z is a direct bond, 0 and especially CH ₂ and _R ^{9 represents} a hydrogen atom, methyl, ethyl or isopropyl.

sowie

und

worin Z; R¹¹, _R ¹², R¹³ und R¹⁴ die in nachfolgender Tabelle angegebenen Bedeutungen haben:

Examples of substituted aromatic radicals are: 4-methyl-1,3-phenylene, 4-ethyl-1,3-phenylene, 2-methyl-1,3-phenylene, 4-benzyl-1,3-phenylene, 4-methoxymethyl -1,3-phenylene, tetrahydro-1,3- or -1,4-naphthylene, 3-propyl-1,3- or -1,4-phenylene, 3-isopropyl-1,4-phenylene, 3.5 -Dimethyl-1,4-phenylene, 2,4-dimethyl-1,3-phenylene, 2,3-dimethyl-1,4-phenylene, 5-methyl-1,3-phenylene, 2,3,5,6 -Tetramethyl-1,4- or -1,3-phenylene, 3-methyl-2,6-pyridylene, 3,5-dimethyl-2,6-pyridylene, 3-ethyl-2,6-pyridylene, 1-methyl -2,7-naphthylene, 1,6-dimethyl-2,7-naphthylene, 1-methyl-2,4-naphthylene, 1,3-dimethyl-2,4-naphthylene, the divalent residues of 5-amino-1- (3'-amino-4'-methylphenyl) -1,3,3- trimethylindan or 6-amino-5-methyl-1- (3'-amino-4'-methyl) -1,3,3-trimethylindan, 4-methoxymethyl-1,3-phenylene, 3-methyl-p-diphenylene, 3-ethyl-p-diphenylene, 3,3'-dimethyl-p-diphenylene, 3,3'-diethyl-p-diphenylene, 3-methyl-3'-ethyl-p-diphenylene, 3,3 ', 5, 5'-tetramethyl-diphenylene, 3,3'-methyl-5,5'-ethyl-p-diphenylene, 4,4'-dimethyl-m-diphenylene, 3,3'-diisopropyldiphenylene, residues of the formulas

such as

and

where Z; R ¹¹ , _R ¹² , R ¹³ and R ^{14 have} the meanings given in the table below:

The diamines from which R or R 'are derived are known or can be prepared by known processes. Diamines with polysiloxane units are known from US Pat. No. 3,435,002 and from EP-A-0 054 426.

The polymers to be used according to the invention have average molecular weights (number average) of at least 2,000, preferably at least 5,000. The upper limit essentially depends on properties that determine processability, such as their solubility. It can be up to 500,000, preferably up to 100,000 and especially up to 60,000. It can also be statistical Act polymers or block polymers. They are manufactured using the usual procedures in the facilities provided for this purpose. The polymers are preferably linear, but can be little branched with at least trifunctional monomers, which are added in small amounts.

The homo- or copolymers are preferably selected from the group of polyimides, polyamides, saturated polyesters, polycarbonates, polyamideimides, polyesterimides, polyesteramides, polysiloxanes, unsaturated polyesters, epoxy resins, aromatic polyethers, aromatic polyether ketones, aromatic polyether sulfones, aromatic polyketones, aromatic polythioethers, aromatic polyimidazoles, aromatic polypyrrones or mixtures of these polymers.

worin A ein vierwertiger organischer Rest und R ein zweiwertiger organischer Rest sind.Among these polymers, a polyimide with recurring structural elements of the formula I, where q = 0, or a copolyimide of recurring structural elements of the formula I, in which q = O, and recurring structural elements of the formula II are very particularly preferred

wherein A is a tetravalent organic radical and R are a divalent organic radical.

_R and _R ¹⁰ in the homo- and copolyimides represent particularly aromatic organic radicals. Of the copolyimides, those are particularly preferred which contain at least 60 mol%, preferably 80 mol%, of structural elements of the formula I.

und

worin R₁₅ ausgewählt wird aus der Gruppe, bestehend aus

A in formula II can be selected as the non-benzophenone radical from the following groups: aromatic, aliphatic, cycloaliphatic, heterocyclic groups, combinations of aromatic and aliphatic groups. The groups can also be substituted. The groups A can be characterized by the following structures:

and

wherein R _{15 is} selected from the group consisting of

Phenylene and -0 (̵R ^d -O) ̵ _b , in which b is 1-10 and R ^{d is} alkylene, cycloalkylene, arylene or aralkylene, where R ₁₆ and R _{17 are} alkyl having preferably 1 to 6 carbon atoms or aryl, especially phenyl , mean. Of the free bonds in the formulas above, there are always two on vicinal carbon atoms.

• 2,3,9,10-Perylentetracarbonsäuredianhydrid,
• 1,4,5,8-Naphthalintetracarbonsäuredianhydrid,
• 2,6-Dichlornaphthalin-1,4,5,8-tetracarbonsäuredianhydrid,
• 2,7-Dichlornaphthalin-1,4,5,8-tetracarbonsäuredianhydrid,
• 2,3,6,7-Tetrachlornaphthalin-1,4,5,8-tetracarbonsäuredianhydrid,
• Phenanthren-l,8,9,10-tetracarbonsäuredianhydrid,
• Pyromellitsäuredianhydrid,
• 3,3',4,4'-Biphenyltetracarbonsäuredianhydrid,
• 2,2',3,3'-Biphenyltetracarbonsäuredianhydrid,
• 4,4'-Isopropylidendiphthalsäureanhydrid,
• 3,3'-Isopropylidendiphthalsäureanhydrid,
• 4,4'-Oxydiphthalsäureanhydrid,
• 4,4'-Sulfonyldiphthalsäureanhydrid,
• 3,3'-Oxydiphthalsäureanhydrid,
• 4,4'-Methylendiphthalsäureanhydrid,
• 4,4'-Thiodiphthalsäureanhydrid,
• 4,4'-Aethylidendiphthalsäureanhydrid,
• 2,3,6,7-Naphthalintetracarbonsäuredianhydrid,
• 1,2,4,5-Naphthalintetracarbonsäuredianhydrid,
• 1,2,5,6-Naphthalintetracarbonsäuredianhydrid,
• Benzol-1,2,3,4-tetracarbonsäuredianhydrid,
• Thiophen-2,3,4,5-tetracarbonsäuredianhydrid,
• 1-(3',4'-Dicarboxyphenyl)-1,3,3-trimethylindan-5,6-dicarbonsäure- dianhydrid,
• 1-(3',4'-Dicarboxyphenyl)-1,3,3-trimethylindan-6,7-dicarbonsäure- dianh^ydrid,
• 1-(3',4'-Dicarboxyphenyl)-3-methylindan-5,6-dicarbonsäure- dianhydrid;
• Tetrahydrofurantetracarbonsäuredianhydrid,
• Cyclopentantetracarbonsäuredianhydrid,
• Cyclooctantetracarbonsäuredianhydrid und
• 1,(3',4'-Dicarboxyphenyl)-3-methylindan-6,7-dicarbonsäuredian- hydrid und Dianhydride der allgemeinen Formel
  
  worin Y_l, Y₂, Y₃ und Y₄ jeweils unter Wasserstoff, Alkyl, besonders Methyl ausgewählt werden.

Suitable tetracarboxylic anhydrides or their esters with a tetravalent radical A are, for example:

• 2,3,9,10-perylenetetracarboxylic dianhydride,
• 1,4,5,8-naphthalenetetracarboxylic acid dianhydride,
• 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride,
• 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride,
• 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride,
• Phenanthrene-1,8,9,10-tetracarboxylic dianhydride,
• Pyromellitic dianhydride,
• 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride,
• 2,2 ', 3,3'-biphenyltetracarboxylic acid dianhydride,
• 4,4'-isopropylidenediphthalic anhydride,
• 3,3'-isopropylidenediphthalic anhydride,
• 4,4'-oxydiphthalic anhydride,
• 4,4'-sulfonyldiphthalic anhydride,
• 3,3'-oxydiphthalic anhydride,
• 4,4'-methylene diphthalic anhydride,
• 4,4'-thiodiphthalic anhydride,
• 4,4'-ethylidene diphthalic anhydride,
• 2,3,6,7-naphthalenetetracarboxylic acid dianhydride,
• 1,2,4,5-naphthalenetetracarboxylic acid dianhydride,
• 1,2,5,6-naphthalenetetracarboxylic dianhydride,
• Benzene-1,2,3,4-tetracarboxylic acid dianhydride,
• Thiophene-2,3,4,5-tetracarboxylic dianhydride,
• 1- (3 ', 4'-dicarboxyphenyl) -1,3,3-trimethylindane-5,6-dicarboxylic acid dianhydride,
• 1- (3 ', 4'-dicarboxyphenyl) -1,3,3-trimethylindan-6,7-dicarboxylic acid dianh ^y drid,
• 1- (3 ', 4'-dicarboxyphenyl) -3-methylindane-5,6-dicarboxylic acid dianhydride;
• Tetrahydrofuran tetracarboxylic dianhydride,
• Cyclopentanetetracarboxylic dianhydride,
• Cyclooctantetracarbonsianianianhydrid and
• 1, (3 ', 4'-dicarboxyphenyl) -3-methylindane-6,7-dicarboxylic acid dianhydride and dianhydrides of the general formula
  
  wherein Y ₁ , Y ₂ , Y ₃ and Y _{4 are} each selected from hydrogen, alkyl, especially methyl.

worin _R15 Methylen, Sauerstoff, Sulfonyl oder

bedeutet.The most preferred non-benzophenone aromatic dianhydrides are pyromellitic dianhydride and aromatic dianhydrides is characterized by the general formula

wherein _{R15 is} methylene, oxygen, sulfonyl or

means.

worin W eine covalente Bindung, Schwefel, Carbonyl, -NH, -N-Alkyl, 0, S, SS, -N-Phenyl, Sulfonyl, eine lineare oder verzweigte Alkylengruppe mit 1 bis 3 Kohlenstoffatomen, Alkyliden mit 2 bis 12 C-Atomen, Cycloalkyliden mit 5 oder 6 Ringkohlenstoffatomen, Arylen, insbesondere die Phenylengruppe, oder eine Dialkyl- oder Diarylsilylgruppe bedeutet und R₁₈ und R₁₉ unabhängig voneinander jeweils Wasserstoff, Halogen, insbesondere Chlor oder Brom, Alkyl mit 1 bis 5 Kohlenstoffatomen, insbesondere Methyl, Alkoxy mit 1 bis 5 Kohlenstoffatomen, insbesondere Methoxy, oder Aryl, insbesondere Phenyl, bedeuten.The group R ¹⁰ defined above can be selected from alkylene groups with 2 to 20 carbon atoms, cycloalkylene groups with 4 to 6 ring carbon atoms; a xylylene group, arylene group selected from meta- or para-phenylene, tolylene, byphenylene, naphthylene or anthrylene; an unsubstituted or substituted arylene group of the formula

wherein W is a covalent bond, sulfur, carbonyl, -NH, -N-alkyl, 0, S, SS, -N-phenyl, sulfonyl, a linear or branched alkylene group with 1 to 3 carbon atoms, alkylidene with 2 to 12 carbon atoms , Cycloalkylidene having 5 or 6 ring carbon atoms, arylene, in particular the phenylene group, or a dialkyl or diarylsilyl group and R ₁₈ and R ₁₉ each independently of one another are hydrogen, halogen, in particular chlorine or bromine, alkyl having 1 to 5 carbon atoms, in particular methyl, alkoxy with 1 to 5 carbon atoms, especially methoxy, or aryl, especially phenyl.

dar, worin W eine covalente Bindung, Methylen, Schwefel, Sauerstoff oder Sulfon darstellt und R₁₈ und R₁₉ unabhängig voneinander Wasserstoff, Halogen oder Alkyl mit 1 bis 5 Kohlenstoffatomen, insbesondere Methyl, bedeuten, oder eine Gruppe der Formel

worin R²¹ Wasserstoff, Halogen oder Alkyl mit 1 bis 5 Kohlenstoffatomen, insbesondere Methyl, bedeutet.More preferably, R ¹⁰ includes groups derived from the aromatic diamines previously described. Most preferably R ^{10 represents} a group of the formula

in which W represents a covalent bond, methylene, sulfur, oxygen or sulfone and R ₁₈ and R ₁₉ independently of one another are hydrogen, halogen or alkyl having 1 to 5 carbon atoms, in particular methyl, or a group of the formula

wherein R ^{21 is} hydrogen, halogen or alkyl having 1 to 5 carbon atoms, especially methyl.

worin W eine kovalente Bindung, Methylen, 2,2-Propyliden, Cyclohexyliden, Schwefel, Sauerstoff oder Sulfon bedeutet.R ¹⁰ is particularly preferably meta- or para-phenylene or a radical of the formula

where W is a covalent bond, methylene, 2,2-propylidene, cyclohexylidene, sulfur, oxygen or sulfone.

• 4,4'-Methylehbis-(o-chloranilin), 3,3'-Dichlorbenzidin, 3,3'-Sulfonyldianilin, 4,4'-Diaminobenzophenon, l,5-Diaminonaphthalin, Bis-(4-aminophenyl)-dimethylsilan, Bis-(4-aminophenyl)-diäthyl- silan, Bis-(4-aminophenyl)-diphenylsilan, Bis-(4-aminophenyloxy)-dimethylsilan, Bis-(4-aminophenyl)-äthylphosphinoxid, N-[Bis-(4-aminophenyl)]-N-methylamin, N-[ßis-(4-aminophenyl)]-N-phenylamin, 4,4'-Methylenbis-(3-methylanilin), 4,4'-Methylenbis-(2-äthyl- anilin), 4,4'-Methylenbis-(2-methoxyanilin), 5,5'-Methylenbis-(2-aminophenol), 4,4'-Methylenbis-(2-methylanilin), 4,4'-Oxybis-(2- methoxyanilin), 4,4'-Oxybis-)2-chloranilin), 5,5'-Oxybis-(2-aminophenol), 4,4'-Thiobis-(2-methylanilin), 4,4'-Thiobis-(2-methoxy- anilin), 4,4'-Thiobis-(2-chloranilin), 4,4'-Sulfonylbis-(2-methylanilin), 4,4'-Sulfonylbis-(2-äthoxyanilin), 4,4'-Sulfonylbis-(2- chloranilin), 5,5'-Sulfonylbis-(2-aminophenol), 3,3'-Dimethyl-4,4'-diaminobenzophenon, 3,3'-Dimethoxy-4,4'-diaminobenzophenon, 3,3'-Dichlor-4,4'-diaminobenzophenon, 4,4'-Diaminobiphenyl, m-Phenylendiamin, p-Phenylendiamin, 4,4'-Methylendianilin, 4,4'-Oxydianilin, 4,4'-Thiodianilin, 4,4'-Sulfonyldianilin, 4,4'-Isopropylidendianilin, 3,3'-Dimethylbenzidin, 3,3'-Dimethoxybenzidin, 3,3'-Dicarboxybenzidin, Diaminotoluol, 4,4'-Methylen-bis-(3-carboxyanilin) und deren Ester.

Examples of diamines with a divalent radical R ¹⁰ are:

• 4,4'-methylhbis- (o-chloroaniline), 3,3'-dichlorobenzidine, 3,3'-sulfonyldianiline, 4,4'-diaminobenzophenone, 1,5-diaminonaphthalene, bis- (4-aminophenyl) dimethylsilane, Bis- (4-aminophenyl) -diethylsilane, bis- (4-aminophenyl) -diphenylsilane, bis- (4-aminophenyloxy) -dimethylsilane, bis- (4-aminophenyl) -ethylphosphine oxide, N- [bis- (4- aminophenyl)] - N-methylamine, N- [ßis (4-aminophenyl)] - N-phenylamine, 4,4'-methylenebis (3-methylaniline), 4,4'-methylenebis (2-ethylaniline) ), 4,4'-methylenebis (2-methoxyaniline), 5,5'-methylenebis (2-aminophenol), 4,4'-methylenebis (2-methylaniline), 4,4'-oxybis- (2nd - methoxyaniline), 4,4'-oxybis-) 2-chloroaniline), 5,5'-oxybis- (2-aminophenol), 4,4'-thiobis (2-methylaniline), 4,4'-thiobis (2-methoxy-aniline), 4,4'-thiobis (2-chloroaniline), 4,4'-sulfonylbis (2-methylaniline), 4,4'-sulfonylbis (2-ethoxyaniline), 4,4 '-Sulfonylbis- (2-chloroaniline), 5,5'-Sulfonylbis- (2-aminophenol), 3,3'-Dimethyl-4,4'-diaminobenzophenone, 3,3'-Dimethoxy-4,4'-diaminobenzophenone , 3,3'-dichloro-4,4'-diaminobenzophenone, 4,4'-diaminobiphenyl, m-phenylenediamine, p-phenylenediamine, 4,4'-methylenedianiline, 4,4'-oxydianiline, 4,4'-thiodianiline , 4,4'-sulfonyldianiline, 4,4'-isopropylidenedianiline, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 3,3'-dicarboxybenzidine, diaminotoluene, 4,4'-methylene-bis- (3- carboxyaniline) and their esters.

und/oder weiteren Diaminen der Formel NH₂R¹⁰NH₂, und anschliessende Imidcyclisierung unter Einwirkung von Carbonsäureanhydriden und/oder anschliessendes Erhitzen. Bei einem weiteren bekannten Verfahren werden Diisocyanate mit Tetracarbonsäuredianhydriden zu Polyimiden umgesetzt.The homo- and copolyimides are prepared in a customary manner by reacting benzophenonetetracarboxylic anhydride with diamines of the formula NH ₂ RNH ₂ , if appropriate together with further tetracarboxylic anhydrides of the formula

and / or further diamines of the formula NH ₂ R ¹⁰ NH ₂ , and subsequent imide cyclization under the action of carboxylic anhydrides and / or subsequent heating. In a further known process, diisocyanates are reacted with tetracarboxylic dianhydrides to give polyimides.

worin R und R' die zuvor angegebene Bedeutung haben, c eine Zahl von 1 bis etwa 500 und Y eine funktionelle Gruppe sind. Solche funktionelle Gruppen können z.B. sein:

• 22 22 22 NHR²², OH, SH, 0-Acyl, COOR , CON(R²²)₂, COC1, COBr,
  
  und Halogen, besonders Cl und Br. R²² steht für ein Wasserstoffatom oder einen gegebenenfalls hydroxylierten Kohlenwasserstoffrest, z.B. Alkyl oder Hydroxyalkyl mit vorzugsweise 1-20, besonders 1-12 C-Atomen, Aralkyl mit vorzugsweise 7-20, besonders 7-16 C-Atomen, Aryl mit vorzugsweise 6-20, besonders 6-16 C-Atomen oder Cycloalkyl mit vorzugsweise 5-7 Ring-C-Atomen. R²³ kann die gleiche Bedeutung wie _R ²² haben oder
  
  bedeuten. Die Acylgruppe kann 1 bis 20, bevorzugt 1-12 C-Atome enthalten.

Functional imide derivatives of benzophenonetetracarboxylic acid are used to prepare the other selected homo- and copolymers. They can be in Formula III

wherein R and R 'have the meaning given above, c is a number from 1 to about 500 and Y is a functional group. Such functional groups can be, for example:

• 22 22 22 NHR ²² , OH, SH, 0-acyl, COOR, CON (R ²² ) ₂ , COC1, COBr,
  
  and halogen, especially Cl and Br. R ²² represents a hydrogen atom or an optionally hydroxylated hydrocarbon radical, for example alkyl or hydroxyalkyl with preferably 1-20, particularly 1-12 C atoms, aralkyl with preferably 7-20, particularly 7-16 C. -Atoms, aryl with preferably 6-20, especially 6-16 carbon atoms or cycloalkyl with preferably 5-7 ring carbon atoms. R ²³ can have the same meaning as _R ²² or
  
  mean. The acyl group can contain 1 to 20, preferably 1-12 C atoms.

The compounds of formula III, in which c = 1, are known in part from DE-A-30 07 445 or can be prepared by analogous processes. getting produced. The introduction of further functional groups such as the glycidyl group is carried out by customary methods.

The compounds of formula III with c> 1 are new and also an object of the invention. They are oligomeric and low molecular weight polyimides with functional end groups. They are obtained by methods analogous to those of polyimides, the size of c being determined by the amount of monomers of the formula YR-NH ₂ used. With these oligomers and low molecular weight polymers, for example, block polymers with polyimide blocks and, for example, polyamide, polyester or other polyimide blocks are obtained.

Another preferred group of polymers for the material according to the invention is a polyamide or copolyamide composed of organic diamines, dicarboxylic acids, LJ-aminocarboxylic acids and diamines or dicarboxylic acids with structural elements of the formula I, in which q = 1 and in which the R- and R'- Amine groups or carboxyl groups are bonded, and from mixtures of the monomers.

The homopolymers can be those whose molecular chains are composed of dicarboxylic acids and diamines with structural elements of the formula I, or those whose molecular chains are composed of dicarboxylic acids or diamines with structural elements of the formula I and organic diamines or dicarboxylic acids which contains no benzophenone residues. The copolyamides contain further diamine or dicarboxylic acid residues or aminocarboxylic acid residues.

Suitable dicarboxylic acids are, for example linear or branched aliph _a - schematic dicarboxylic acids having preferably 2 to 20, particularly 4 to 16 carbon atoms, unsubstituted or especially alkyl-substituted cycloaliphatic dicarboxylic acids having 5 to 7 ring carbon atoms and unsubstituted or, for example by alkyl, Cl or bromine-substituted aromatic dicarboxylic acids with preferably 8 to 22 carbon atoms. Examples are: malonic acid, adipic acid, trimethyladipic acid, Pimelic acid, suberic acid, azelaic acid, dodecanedicarboxylic acid, cyclohexanedicarboxylic acids, isophthalic acid, terephthalic acid, p-diphenyldicarboxylic acid, bis (4-carboxylphenyl) ether or bis (4-carboxylphenyl sulfone.

Suitable diamines are, for example, linear or branched aliphatic diamines with preferably 2 to 30, especially 4 to 20 C atoms, unsubstituted or substituted by alkyl, especially methyl, cycloaliphatic diamines with preferably 5 to 7 ring C atoms, araliphatic diamines with preferably 7 to 24 carbon atoms and aromatic diamines having 6 to 22, preferably 6 to 18 carbon atoms, which may be unsubstituted or especially substituted by alkyl. Examples are: ethylenediamine, propylenediamine, 1,3- or 1,4-butylenediamine, pentylenediamine, 1,6-hexylenediamine, octylenediamine, decylenediamine, dodecylenediamine, 1,10-alkyl substituted 1,10 _- decylenediamines such as 1,10-dimethyl -1,10-decylenediamine or 1,10-di-n-hexyl-1,10-decylenediamine, xylylenediamine, isophoronediamine, 1,3- or 1,4-cyclohexanediamine, 1,3- or 1,4-phenylenediamine, methylphenylene -diamine, toluenediamine, p-biphenylenediamine, bis (p-aminophenyl) ether, bis _- (p-aminophenyl) sulfone, bis - (- p-aminophenyl) methane.

The amino carboxylic acids can be aromatic, cycloaliphatic or aliphatic amino carboxylic acids, e.g. Aminobenzoic acid, aminocyclohexane carboxylic acid and W-aminocarboxylic acids such as ε-aminocaproic acid or 11-aminoundecanoic acid.

Another preferred group of polymers for the material according to the invention is a polyester or copolyester of organic diols, dicarboxylic acids, hydroxycarboxylic acids and diols or dicarboxylic acids with structural elements of the formula I, in which q = 1 and in which the R and R 'groups are hydroxyl or carboxyl groups are bound, and from mixtures of the monomers.

The homopolyesters can be those whose molecular chains are composed of diols and dicarboxylic acids of the formula III, or those whose molecular chains are composed of dicarboxylic acids or diols of the formula III and organic diols or dicarboxylic acids which contain no benzophenone radicals. The copolyesters contain further residues of dicarboxylic acids, diols and / or hydroxycarboxylic acids.

Suitable dicarboxylic acids have been mentioned previously. Polyesters based on aromatic dicarboxylic acids, especially terphthalic acid and / or isophthalic acid, are preferred. Suitable diols are cycloaliphatic diols such as 1,4-cyclohexanediol, aromatic diols such as bisphenol-A and particularly optionally substituted aliphatic diols such as branched and particularly linear alkylene diols with e.g. 2 to 12, preferably 2 to 6 carbon atoms and 1,4-bis-hydroxymethylcyclohexane and hydroxypivalic acid neopentyl glycol ester in question. Ethylene, trimethylene, tetramethylene and hexamethylene glycol are particularly preferred. Examples of hydroxycarboxylic acids are m- or p-hydroxybenzoic acid or aliphaticew-hydroxycarboxylic acids such as e.g. y-hydroxyvaleric acid, hydroxypivalic acid and e-caprolactone in question.

In a further preferred embodiment, the polymers for the material according to the invention are a polyamideimide or a polyesterimide. Such polymers can be obtained by incorporating tricarboxylic acids of the formula IV or their polymer-forming derivatives, such as esters, anhydrides or acid halides:

The trivalent radical can be a hydrocarbon radical with preferably 6 to 16 carbon atoms, in which two carboxyl groups are bonded to two adjacent carbon atoms. Trimellitic acid is preferred.

The polyamideimides can only be composed of diamines of the formula III and tricarboxylic acids of the formula IV. Copolymers are obtained if dicarboxylic acids and / or diamines, such as those e.g. previously mentioned for the polyamides, also used in the preparation of the polyamideimides, also those of the formula III.

Polyesterimides are obtainable by first reacting an aminocarboxylic acid or an amino alcohol with tricarboxylic acids of the formula IV to form dicarboxylic acids or hydroxycarboxylic acids and then further polycondensing them with diols and / or dicarboxylic acids of the formula III to give polyesters. Here too, additional dicarboxylic acids and / or diols can also be used to prepare copolymers.

Polyester amides are also preferred. These polymers are obtained when dicarboxylic acids of the formula III and / or further dicarboxylic acids are polycondensed with diols of the formula III and / or other diols and diamines of the formula III and / or other diamines, the individual monomers having already been mentioned above.

The N atoms of the amide groups in the aforementioned polymers can be replaced by alkyl having preferably 1 to 6 C atoms, aryl such as e.g. Phenyl, aralkyl such as e.g. Benzyl or cycloalkyl such as e.g. Cyclohexyl to be substituted.

• a) Polysiloxane aus Diolen der Formel III und gegebenenfalls weiteren Diolen und Silanen der Formel (R²⁴)₂SiB₂, worin _R ²⁴ bevorzugt Alkyl mit 1 bis 6 C-Atomen, besonders Methyl, Cycloalkyl, besonders Phenyl ist, und B, Br und besonders Cl oder Alkoxy sowie Aryloxy mit bevorzugt 1 bis 6 C-Atomen, besonders Methoxy oder Phenoxy steht. Diese Polymere können somit Strukturelemente der Formel
  
  und gegebenenfalls der Formel
  
  enthalten, worin E dem Rest der Formel I entspricht, worin q = 1 ist, und E' der zweiwertige Rest eines Dioles ist. In Frage kommende Diole HOE'OH wurden schon zuvor erwähnt. Ferner können diese Polymeren zusätzliche Blöcke mit Strukturelementen der Formel
  
  enthalten, wobei diese Blöcke bis zu 50 Mol.-% ausmachen können, bezogen auf das Polymer.
• b) Ungesättigte Polyester aus ungesättigten Dicarbonsäuren, besonders Maleinsäure und Diolen der Formel I (HOEOH) und gegebenenfalls weiteren Dicarbonsäuren, auch der Formel I und weiteren Diolen HOE'OH. Geeignete Dicarbonsäuren wurden bereits zuvor erwähnt. Diese Polymeren können somit Strukturelemente der Formel
  
  enthalten, worin E" der zweiwertige Rest einer äthylenisch ungesättigten Dicarbonsäure ist.Als weitere Strukturelemente können
  
  und
  
  enthalten sein, worin E"' der zweiwertige Rest einer Dicarbonsäure der Formel I oder einer anderen Dicarbonsäure ist. Diese Polymeren können zusätzlich thermisch in Gegenwart üblicher Polymerisationskatalysatoren durch die Anwesenheit der äthylenisch ungesättigten Gruppen polymerisiert werden, gegebenenfalls zusammen mit reaktiven Verdünnern wie Styrol.
• c) Geeignete Epoxidharze sind auf verschiedene Weise erhältlich. So können die Epoxidverbindungen der Formel III alleine oder zusammen mit weiteren Polyepoxidverbindungen mit mehr als einer Epoxidgruppe im Molekül katalytische z.B. mit tertiären Aminen zu Polyäthern umgesetzt werden oder sie können mit üblichen Härtern wie Polyolen, Polycarbonsäuren und deren Anhydriden oder Polyaminen reagiert werden. Als Härter können auch die Diamine, Diole und Dicarbonsäuren der Formel III verwendet werden, wobei dann auch nur übliche Polyepoxidverbindungen ohne Benzophenontetracarbonsäurereste verwendet werden können. Die Epoxidharze können als Präpolymere verwendet werden, die man nach der Bestrahlung thermisch aushärten kann.
• d) Aromatische Polyäther sind z.B. durch die Umsetzung von Verbindungen der Formel III, worin Y = OH bzw. Halogen, besonders Br oder Cl ist, und R und R' ein aromatischer Rest bedeuten, mit phenylaromatischen Dichloriden oder Bromiden bzw. Diolen erhältlich. Geeignete Halogenide bzw. Diole sind z.B. ein- oder zweikernige phenylaromatische Derivate wie Hydrochinon, p-Dichlor-oder p-Dibromphenylen, p-Dihydroxyphenylen, p-Dichlor- oder p-Dibrodiphenylen, Bis(-p-Hydroxyphenyl)äther, Bis-(p-Chlorphenyl)äther. Die phenylaromatischen Reste können weitere Substituenten enthalten, wie z.B. Alkyl mit bevorzugt 1 bis 4 C-Atomen enthalten. Verwendet man zweikernige phenylaromatische Reste, bei denen die Phenylgruppen an eine Sulfongruppe gebunden sind, so erhält man Polyäthersulfone. Beispiele für solche Derivate sind Bis(p-Chlorphenyl)-sulfon und Bis(p-hydroxyphenyl)sulfon. Polyäther, die nur Strukturelemente der Formel I enthalten, erhält man aus Verbindungen der Formel II_I, worin Y = OH ist, mit Verbindungen der Formel III,worin Y = Halogen ist.
• e) Aromatische Polyketone sind erhältlich durch die Umsetzung von aromatischen Verbindungen der Formel III, worin Y = H ist, mit aromatischen Säurehalogeniden der Formel III, worin Y eine Säurehalogenidgruppe, besonders eine Säurechloridgruppe bedeutet, in Gegenwart von Lewis-Säuren. Zusätzlich können weitere aromatische, -besonders phenylaromatische Verbindungen und/oder aromatische, besonders phenylaromatische Dicarbonsäuredihalogenide mitverwendet werden. Bei den aromatischen Verbindungen handelt es sich bevorzugt um ein- oder zweikernige Phenylaromaten bzw. um ihre Dicarbonsäuredihalogenidderivate. Beispiele sind Benzol, Toluol, Diphenyl, Diphenylmethan, Diphenylketon, Diphenylsulfon, Diphenyläther, Terephthalsäuredichlorid, 4,4'-Chlorcarbonyldiphenyl, -diphenylmethan, -diphenyläther oder -diphenylsulfon. Bei Verwendung der Aetherderivate erhält man Polyätherketone. Die aromatischen Kohlenwasserstoffe bzw. Dicarbonsäuredihalogenide können substituiert sien, z.B. mit Alkyl mit 1 bis 4 C-Atomen.
• f) Aromatische Polythioäther sind z.B. erhältlich durch die Umsetzung von aromatischen Verbindungen der Formel III, worin Y = Halogen wie Cl und besonders Br ist, mit Dialkalisulfiden, z.B. Na_ZS. Es können auch andere aromatische, besonders phenylaromatisch Dihalogenverbindungen, bevorzugt Chloride und besonders Bromide mitverwendet werden. Aromatische Polysulfide sind auch erhältlich durch die Umsetzung von aromatischen Verbindungen der Formel III, worin Y = SH ist, alleine oder zusammen mit anderen besonders phenylaromatischen Dimerkaptanen,bzw. besonders deren Alkalisalzen wie z.B. der Natriumsalze, mit Verbindungen der Formel III, worin Y für Halogen, besonders Br steht, und/oder anderen besonders phenylaromatischen Dihalogeniden, wie z.B. Bromiden. Solche Halogenide wurden schon zuvor erwähnt. Geeignete aromatische Dimercaptane sind z.B. 1,4-Phenylendimerkaptan oder p-Biphenylendimerkaptan.
• g) Weitere geeignete Polymere sind z.B. solche, die durch die Umsetzung von Verbindungen der Formel III, worin Y für OH, NH₂ oder COOH steht, mit Diisocyanaten oder Diepoxyden erhältlich sind.
• h) Eine weitere Gruppe geeigneter Polymeren sind aromatische Polyimidazole. Sie sind erhältlich durch Umsetzung von Estern der Formel III alleine oder zusammen mit weiteren aromatischen Dicarbonsäurediestern und aromatischen Tetraminen, z.B. 3,3',4,4'-Tetraaminobiphenyl, zu Polyamidvorstufen, die dann durch Erhitzen zu den Polyimidazolen kondensiert werden.
• i) Eine weitere Gruppe geeigneter Polymere sind aromatische Polypyrrone. Sie sind z.B. erhältlich durch die Umsetzung von Tetracarbonsäureanhydriden der Formel V
  
  worin R die zuvor gegebene Bedeutung hat und d für eine Zahl von 1 bis 500 steht, mit aromatischen Tetraminen, wie z.B. 3,3',4,4'-Tetraaminodiphenyl. Hierbei werden zunächst lösliche Vorstufen gebildet, die durch Erhitzen zu Polypyrronen polykondensiert werden. Die Verbindungen der Formel V sind erhältlich durch die Reaktion eines Ueberschusses von Benzophenontetracarbonsäuredianhydrid mit Diaminen der Formel H₂NRNH₂. Diese Verbindungen können z.B. auch zur Herstellung von Polyimiden verwendet werden.

Other suitable polymers for the coated material according to the invention are, for example:

• a) polysiloxanes from diols of the formula III and optionally further diols and silanes of the formula (R ²⁴ ) ₂ SiB ₂ , in which _R ^{24 is} preferably alkyl having 1 to 6 carbon atoms, especially methyl, cycloalkyl, especially phenyl, and B, Br and especially Cl or alkoxy and aryloxy with preferably 1 to 6 carbon atoms, especially methoxy or phenoxy. These polymers can thus have structural elements of the formula
  
  and optionally the formula
  
  contain, where E corresponds to the rest of the formula I, where q = 1, and E 'is the divalent radical of a diol. Possible diols HOE'OH have already been mentioned. Furthermore, these polymers can contain additional blocks with structural elements of the formula
  
  included, these blocks can make up to 50 mol%, based on the polymer.
• b) Unsaturated polyesters from unsaturated dicarboxylic acids, especially maleic acid and diols of the formula I (HOEOH) and optionally further dicarboxylic acids, also of the formula I and further diols HOE'OH. Suitable dicarboxylic acids have already been mentioned. These polymers can thus have structural elements of the formula
  
  contain, wherein E "is the divalent radical of an ethylenically unsaturated dicarboxylic acid. As further structural elements can
  
  and
  
  be contained, in which E "'is the divalent radical of a dicarboxylic acid of the formula I or another dicarboxylic acid. These polymers can additionally be thermally polymerized in the presence of customary polymerization catalysts by the presence of the ethylenically unsaturated groups, optionally together with reactive diluents such as styrene.
• c) Suitable epoxy resins are available in various ways. For example, the epoxy compounds of the formula III can be reacted alone or together with other polyepoxide compounds with more than one epoxide group in the molecule, for example with tertiary amines to form polyethers, or they can be reacted with conventional hardeners such as polyols, polycarboxylic acids and their anhydrides or polyamines. The diamines, diols and dicarboxylic acids of the formula III can also be used as hardeners, it then also being possible to use only conventional polyepoxide compounds without benzophenonetetracarboxylic acid residues. The epoxy resins can be used as prepolymers which can be cured thermally after the irradiation.
• d) Aromatic polyethers can be obtained, for example, by reacting compounds of the formula III in which Y = OH or halogen, in particular Br or Cl, and R and R 'are an aromatic radical, with phenylaromatic dichlorides or bromides or diols. Suitable halides or diols are, for example, mono- or dinuclear phenylaromatic derivatives such as hydroquinone, p-dichloro- or p-dibromophenylene, p-dihydroxyphenylene, p-dichloro- or p-dibrodiphenylene, bis (-p-hydroxyphenyl) ether, bis ( p-chlorophenyl) ether. The phenylaromatic radicals can contain further substituents, such as, for example, alkyl having preferably 1 to 4 carbon atoms. If dinuclear phenylaromatic radicals are used in which the phenyl groups are bonded to a sulfone group, polyether sulfones are obtained. Examples of such derivatives are bis (p-chlorophenyl) sulfone and bis (p-hydroxyphenyl) sulfone. Polyether that only structural elements containing the formula I is obtained from compounds of the formula II _I in which Y = OH, with compounds of the formula III in which Y = halogen.
• e) Aromatic polyketones can be obtained by reacting aromatic compounds of the formula III, in which Y = H, with aromatic acid halides of the formula III, in which Y is an acid halide group, in particular an acid chloride group, in the presence of Lewis acids. In addition, other aromatic, especially phenylaromatic compounds and / or aromatic, especially phenylaromatic dicarboxylic acid dihalides can also be used. The aromatic compounds are preferably mono- or dinuclear phenyl aromatics or their dicarboxylic acid dihalide derivatives. Examples are benzene, toluene, diphenyl, diphenyl methane, diphenyl ketone, diphenyl sulfone, diphenyl ether, terephthalic acid dichloride, 4,4'-chlorocarbonyl diphenyl, diphenyl methane, diphenyl ether or diphenyl sulfone. When using the ether derivatives, polyether ketones are obtained. The aromatic hydrocarbons or dicarboxylic acid dihalides can be substituted, for example with alkyl having 1 to 4 carbon atoms.
• f) Aromatic polythioethers can be obtained, for example, by reacting aromatic compounds of the formula III, in which Y = halogen such as Cl and especially Br, with dialkali sulfides, for example Na _Z S. Other aromatic, especially phenylaromatic dihalogen compounds, preferably chlorides and especially Bromides can be used. Aromatic polysulfides can also be obtained by reacting aromatic compounds of the formula III, in which Y = SH, alone or together with other particularly phenylaromatic dimercaptans, or. especially their alkali metal salts, such as the sodium salts, with compounds of the formula III in which Y is halogen, in particular Br, and / or others in particular phenyl aromatic dihalides, such as bromides. Such halides have been mentioned before. Suitable aromatic dimercaptans are, for example, 1,4-phenylene dimercaptan or p-biphenylene dimercaptan.
• g) Other suitable polymers are, for example, those which can be obtained by reacting compounds of the formula III in which Y is OH, NH ₂ or COOH with diisocyanates or diepoxides.
• h) Another group of suitable polymers are aromatic polyimidazoles. They are obtainable by reacting esters of the formula III alone or together with other aromatic dicarboxylic acid diesters and aromatic tetramines, for example 3,3 ', 4,4'-tetraaminobiphenyl, to give polyamide precursors which are then condensed to the polyimidazoles by heating.
• i) Another group of suitable polymers are aromatic polypyrrones. They can be obtained, for example, by the reaction of tetracarboxylic anhydrides of the formula V
  
  wherein R has the meaning given above and d stands for a number from 1 to 500, with aromatic tetramines, such as 3,3 ', 4,4'-tetraaminodiphenyl. Soluble precursors are initially formed, which are polycondensed by heating to form polypyrrons. The compounds of the formula V can be obtained by reacting an excess of benzophenonetetracarboxylic acid dianhydride with diamines of the formula H ₂ NRNH ₂ . These compounds can also be used, for example, for the production of polyimides.

To produce the coated material according to the invention, the polymer or mixtures thereof is expediently dissolved in a suitable organic solvent, if appropriate with heating. Suitable solvents are e.g. polar, aprotic solvents that can be used alone or in mixtures of at least two solvents. Examples are: ethers such as dibutyl ether, tetrahydrofuran, dioxane, methylene glycol, dimethyl ethylene glycol, dimethyl diethylene glycol, diethyl ethylene glycol, dimethyltriethylene glycol, halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2- Tetrachloroethane, carboxylic acid esters and lactones such as ethyl acetate, methyl propionate, ethyl benzoate, 2-methoxyethyl acetate, y-butyrolactone, o-valerolactene and pivalolactone, carboxamides and lactams such as formamide, acetamide, N-methylformethylformamide, N, N-dimethylformamide, N, N-N-formamide N, N-dimethylacetamide, N, N-diethyl-acetamide, γ-butyrolactam, ε-caprolactam, N-methypyrrolidone, N-acetylpyrrolidone, N-methylcaprolactam, tetramethylurea, hexamethylphosphoric acid amide, sulfoxides such as dimethyl sulfoxide, sulfone, dimethyl sulfone such as dimethyl sulfone such as dimethyl sulfone, Tetramethylene sulfone, trimethylamine, triethylamine, N-methylpyrrolidine, N-methylpiperidine, N-methylmorpholine, substituted B enzenes such as chlorobenzene, nitrobenzene, phenols or cresol. In the case of insoluble polymers, soluble precursors can be used, which are then irradiated after coating and then converted into polymers by heating.

Undissolved parts can be removed by filtration, preferably pressure filtration. The concentration of polymer in the coating composition thus obtained is preferably not more than 50% by weight, particularly not more than 30% by weight and in particular not more than 20% by weight, based on the solution. Coating agents with polymers with structural elements of the formula I, in which R or R ' an aromatic radical or araliphatic radical which is substituted as defined are new and likewise an object of the invention.

Further customary additives which do not negatively influence the sensitivity to light can be incorporated in the preparation of the solutions. Examples of these are matting agents, leveling agents, finely divided fillers, flame retardants, optical brighteners, antioxidants, light stabilizers, stabilizers, dyes, pigments and adhesion promoters. Furthermore, if desired, additional sensitizers such as e.g. Thioxanthone derivatives or benzophenone derivatives are incorporated in order to increase the sensitivity to light even further, as well as antihalo dyes such as those e.g. are described in U.S. Patent 4,349,619.

The coating agent can be applied to suitable substrates or carrier materials by means of customary methods, such as dipping, brushing and spraying methods, centrifugal, cascade casting and curtain casting coating. Suitable substrates are, for example, plastics, metals and metal alloys, semimetals, semiconductors, glass, ceramics and other inorganic materials such as Si0 ₂ and Si ₃ N ₄ . The solvent is then removed, if appropriate by heating and, if appropriate, in vacuo. Tack-free, dry and uniform films are obtained. The films applied can. Depending on the application, layer thicknesses of up to approximately 500 μm and more, preferably from 0.5 to 500 μm and particularly from 1 to 50 μm.

The radiation-sensitive layer in the material according to the invention can be crosslinked by the action of radiation.

The photostructuring or photo crosslinking can be brought about by high-energy radiation, for example by light, in particular in the UV range, by means of X-rays, laser light, electron beams, etc. The material according to the invention is outstandingly suitable for use in manufacturing provision of protective films, passivating varnishes, and as photographic recording material for thermostable relief images.

Another object of the invention is this use. Areas of application are e.g. Protective, insulating and passivating varnishes in electrical engineering and electronics, photomasks for electronics, textile printing and the graphics industry, etching resist for the production of printed circuits and printing plates and integrated circuits, relays for the production of X-ray masks, as a release mask, as a dielectric for multilayer circuits , as a structural element for liquid crystal displays.

Protective films are produced by direct exposure, the exposure times essentially depending on the layer thicknesses and light sensitivity.

The relief structure is photographically produced by imagewise exposure through a photomask, followed by development with removal of the unexposed portions using a solvent or a solvent mixture, after which the image formed can optionally be stabilized by a thermal aftertreatment.

Another object of the invention is such a method for applying relief structures. As developers are e.g. the aforementioned solvents are suitable.

The polymer layer of the material according to the invention has a sufficient and in some cases high sensitivity to light for many purposes and it can be directly photocrosslinked. The Protective films and relief images are characterized by no adhesive strength and thermal, mechanical and chemical resistance, especially those made of polyimide layers. Only slight shrinkage is observed with thermal aftertreatments. Furthermore, additives for generating or increasing photosensitivity can be avoided. The material is stable in storage, but must be protected from exposure to light.

The following examples explain the invention in more detail.

A) Production of the starting products

• Example 1: In a cylindrical vessel equipped with a stirrer, dropping funnel, internal thermometer and nitrogen inlet tube, 27.28 g (0.12 mol) of 4,4'-diamino-3,3'-dimethyldiphenylmethane in 370 are added under nitrogen g of N-methylpyrrolidone (NMP) dissolved and cooled to 0 to 5 ° C. 39.43 g (0.1225 mol) of benzophenonetetracarboxylic acid dianhydride (BTDA) are now provided and added in portions over the course of 4 hours. 30 minutes after the last addition, 48.48 g of triethylamine (0.48 mol) and 110.1 g (1.08 mol) of acetic anhydride are added dropwise in order to cyclize the resulting polyamic acid to the polyimide. After 16 hours of stirring at room temperature, the solution is poured onto 6 l of water with vigorous stirring and the precipitated product is filtered off. The product is treated again with 6 l of water, filtered and dried at 80 ° C. in vacuo. The inherent viscosity, measured as a 0.5% solution in NMP at 25 ° C, is 0.97 dl / g. The glass transition temperature (Tg), measured by differential scanning calometry (DSC), is 285 ° C.
• Example 2: The procedure is as in Example 1, but a mixture of 66.7 mol% BTDA and 33.3 mol% pyromellitic dianhydride (PMDA) is used. Properties of the copolyimide obtained:
  
  
• Example 3: The procedure of Example 1 is ethyl-3-4.4 implement a technical mixture of 3,3'-diethyl-4,4'-diaminodiphenylmcthan, ^{1-diaminodiphenylmethane} and 4,4'-diaminodiphenylmethane with a stoichiometric amount of BTDA and Cyclized polyimide.
  
  
• Example 4: Example 3 is repeated with a mixture of 50 mol% BTDA and 50 mol% PMDA. The copolyimide obtained has the following properties:
• 
  
  Example 5: In a condensation apparatus as described in Example 1, a solution of 4.02 g of diamine mixture according to Example 3 in NMP as solvent with 3.78 g of BTDA (molar ratio of diamine mixture to BTDA = 3: 2) is condensed to a polyamic acid block with amino end groups . The solution is then cooled to -15 ° C. and then first 3.5717 g of isophthalic acid dichloride and then 2.6791 g of diamine mixture are added (molar ratio of isophthalic acid dichloride: diamine mixture = 3: 2). Removing the cooling gradually increases the temperature to room temperature. After 5 hours, 3 ml of propylene oxide and after another half an hour, 6.51 g of triethylamine and 26.6 g of acetic anhydride are added. The mixture is stirred overnight and the block copolyamideimide is precipitated the next day by stirring it into water. Characteristics:
  
  
• Example 6: According to Example 1, a mixture of 4,4'-diaminodiphenylmethane and 2,4-diaminotoluene (molar ratio 19.7: 80.3) is polycondensed with the equivalent amount of BTDA. Properties of the polyimide:
  
  
• Example 7: According to Example 1, a mixture of 2,4-diaminotoluene and 5, (6) -amino-1- (4-aminophenyl) -1,3,3-trimethylindane (molar ratio 54.4: 45.6 ) polycondensed with an equivalent amount of BTDA. Properties of the copolyimide:
  
  
• Examples 8 and 9: Analogously to Example 1, polyimides are obtained by polycondensation of BTDA with an equivalent amount of 2-amino-6-methyl-6- (4-aminophenyl) heptane or 2-amino-6-methyl-6- (3- Ethyl-4-aminophenyl) heptane produced. Properties of the polyimides:
  
  
• Example 10: A mixture of 13.21 g (0.038 mol) of 1,10-diamino-1,10-di-n-hexyldecane and 13.34 g of BTDA (0.038 mol.) Is placed in a sulfonation flask equipped with a stirrer, internal thermometer, nitrogen inlet tube and water separator ) in 100 ml o-dichlorobenzene for 30 min. stirred for a long time under nitrogen. Then the mixture is slowly heated to reflux temperature (175 ° C), whereby a clear light yellow solution is formed. In the course of 90 min. the water of condensation is distilled off together with o-dichlorobenzene and separated off in a water separator.
  A sample for analytical purposes is isolated by stirring part of the cooled solution in hexane, filtering off and drying. Properties of the polyimide:
  
  
• Examples 11-20: According to Example 1, the following diamines are polycondensed with BTDA to form polyimides and the properties of the polymers are determined.
  
  
• Example 21: (polyimide from isocyanate and anhydride) 0.7905 g (0.0021 mol) of N, N'-di- (3-isocyanato-4-methyl) -phenyl-parabanoic acid are placed in a reaction vessel with stirrer, reflux condenser and gas inlet , 1.4633 g (0.0084 mol) of toluene-2,4-diisocyanate in DMSO (23 ml) at room temperature under N ₂ and 3.386 g (0.0105 mol) of benzophenonetetracarboxylic acid dianhydride were added. The mixture is heated to 90 ° C. and kept at this temperature for 24 hours. After cooling, the solution is stirred into water and the polymer is precipitated. η = 0.228 dl / g. Tg = 349 ° C
• Example 22: (polyimide / polyesteramide) 1.5 g (7.39 mmol) of isophthalic acid dichloride are dissolved in 38 ml of N-methylpyrrolidone (DMP) in a reaction vessel and cooled to -15 ° C. Then 0.537 g (4.92 mmol) of m-aminophenol and 1.4 ml of triethylamine are added. After 30 minutes, 2.832 g (17.2 mmol) of 3,6-diaminodurol and 0.65 ml of triethylamine are added. By removing the cooling bath, the temperature is allowed to rise to 0 ° C. and 4.76 g (14.78 mmol) of BTDA are added. After 8 hours of stirring at room temperature, the polyamic acid is cyclized to the polyimide by adding 4.5 ml of triethylamine and 12.6 ml of acetic anhydride for 16 hours and worked up as usual. η = 0.38 dl / g
• Example 23: (polyimide / polycarbonate) Under the same conditions as in Example 26, the following components are reacted with one another in the following order:
  • 0.008 mol of phosgene,
  • 0.0053 mol bisphenol A,
  • 0.01866 moles of mesitylenediamine and
  • 0.016 mole BTDA.
    
    
• Example 24: (Polyimide / polyamideimide) 7.5 mmol of 4,4'-diamino-3,5,3 ', 5'-tetraethyldiphenylmethane and 2.5 mmol of 4,4'-diaminodiphenylmethane are dissolved in 25 ml of NMP, the solution cooled to -15 ° C and reacted with 2.5 mmol of trimellitic anhydride chloride in the presence of 0.4 ml of triethylamine. The resulting prepolymer is then reacted further with 7.5 mmol BTDA and then cyclized with triethylamine and acetic anhydride.
  
  
• Example 25: (Polyimide ester) 20 mmol of 3-amino-6-hydroxydurol are reacted in 34.5 ml of NNP at 0 ° C. with 0.01 mol of BTDA. Then 0.01 mol of isophthalic acid dichloride and 6.1 ml of triethylamine are added at -15 ° C. After 15 minutes, the cooling is removed and stirring is continued for 8 hours at room temperature. The cyclization takes place with acetic anhydride
  
  
• Example 26c (polyimide / polyphenylene sulfide) 1.6458 g 3,6-diaminodurol and 0.9333 g of a polyphenylene sulfide with amino end groups [manufactured according to Polymer Bulletin 4, 459-466 (1981)] are in 24 ml NMP with 3.4313 g BTDA reacted at 0 to 25 ° C for 24 hours and then cyclized with triethylamine and acetic anhydride.
  
  
• Example 27: (Polyimide / polyether sulfone) The polyether sulfone with amino end groups used for this purpose is produced by condensation of 4,4'-dichlorodiphenyl sulfone, bisphenol A and 4-chloronitrobenzene in the presence of potassium carbonate in DMF and subsequent reduction of the terminal nitro groups. Analogously to Example 26, 3.018 g of 3,6-diaminodurol and 1,796 g of the polyether sulfone are reacted with 6.231 g of BTDA in 44 ml of NMP and cyclized to give the polyimide.
  
  

B) Examples of use

A thin polymer film is created on a copper-clad plastic plate by spinning on a 5% polymer solution and then removing the solvent in a forced air oven. Acetophenone (polymers from Examples 1, 2 and 4), butyrolactone (Example 3), o-dichlorobenzene (Example 10 without isolation of the polymer) and N-methylpyrrolidone are used as solvents in the polymers of the other examples.

The plates coated in this way are exposed through a photomask (Stouffer wedge) at room temperature with a 1,000 watt UV lamp from a distance of 18 cm. The exposed plates are then developed with a solvent, the unexposed portions of the polymer film being dissolved away. The relief image is then made visible by etching away the exposed copper layer with FeCl ₃ solution.

The exposure time, the developer used and the light sensitivity are given in the table below. MEK is methyl ethyl ketone, DMF is dimethylformamide.

Claims (17)

1. Coated material from a support onto which a radiation-sensitive polymer is applied as a layer, characterized in that the polymer is a homo- or copolymer with at least 5 mol.-X, based on the polymer, structural units of the formula I,

wherein R is an unsubstituted or substituted divalent aliphatic radical which may be interrupted by hetero atoms, aromatic, heterocyclic or cycloaliphatic groups, an unsubstituted or substituted cycloaliphatic or araliphatic radical, an aromatic radical in which two Ar ^y are lkerne linked via an aliphatic group, or an aromatic radical substituted by at least one alkyl group, cycloalkyl group, alkoxy group, alkoxyalkyl group, alkylthio group, alkylthioalkyl group, hydroxyalkyl group, hydroxyalkoxy group, hydroxyalkylthio group, aralkyl group or two adjacent C atoms of the aromatic radical by an alkylene group, R 'independently has the same meaning as R. and q represents 0 or 1, where R as aromatic radical is not substituted by alkylene and not in both ortho positions to the N atom by the aforementioned radicals if q = 0. 2. Material according to claim 1, characterized in that the homo- or copolymer contains 5 to 100 mol% of structural units of the formula I, based on the polymer. 3. Material according to claim 1, characterized in that the substituent on the aromatic radical contains 1 to 20 carbon atoms. 4. Material according to claim 3, characterized in that the substituent is alkyl, alkoxy or alkoxyalkyl having 1 to 6 carbon atoms, benzyl or trimethylene or tetramethylene. 5. Material according to claim 1, characterized in that one or two substituents in the aromatic radical are bonded ortho to the N atom. 6. Material according to claim 1, characterized in that R as an aliphatic radical 2 to 30 carbon atoms, as a cycloaliphatic radical 5 to 8 ring carbon atoms, as an araliphatic radical 7 to 30 carbon atoms and as a substituted aromatic radical 7 to Contains 30 carbon atoms. 7. Material according to claim 1, characterized in that R as an aliphatic radical is linear or branched alkylene, which by oxygen atoms, NH, NR ^a or ^⊕ NR ^a ₂ G ^⊖ , wherein R ^{a is} alkyl having 1 to 12 carbon atoms or cycloalkyl with 5 or 6 ring C atoms, phenyl or benzyl and G is the anion of a protonic acid, cyclohexylene, naphthylene, phenylene or hydantoins can be interrupted, R as a cycloaliphatic radical is unsubstituted or alkyl-substituted mono- or bicyclic cycloalkylene with 5 to 7 ring C atoms, R as the araliphatic radical is aralkylene which is unsubstituted or substituted on the aryl by alkyl, where the alkylene radical can be linear or branched, and R as the aromatic radical is a hydrocarbon radical or pyridine radical which is substituted by alkyl, alkoxy, alkoxyalkyl, trimethylene , Tetramethylene is substituted. 8. Material according to claim 7, characterized in that R as an aliphatic radical is linear or branched alkylene having 6 to 30 C atoms, - (CH ₂ ) _m -R ¹ - (CH ₂ ) _n -, wherein R ^{1 is} phenylene, naphthylene, cyclopentylene or cyclohexylene and m and n are independently a number of 1, 2 or 3, -R ² (̵OR ³ ) ̵ _p -OR ² -, wherein R ^{2 is} ethylene, 1,2-propylene, 1,3-propylene or 2-methyl-1,3-propylene and R is ethylene, 1,2-propylene, 1,2 -Butylene, 1,3-propylene or 1,4-butylene and p are a number from 1 to 100, or

is. 9. Material according to claim 7, characterized in that R is a cycloaliphatic radical of such formulas

or

are in which q is 0 or 1, R ^{4 is} independently hydrogen or alkyl having 1 to 6 carbon atoms, and X for a direct bond, 0, S, alkylene having 1 to 3 carbon atoms or alkylidene having 2 to 6 carbon atoms -Atoms stands. _10th Material according to claim 7, characterized in that the araliphatic radical of the formula

corresponds, in which the R ⁴ independently represent a hydrogen atom or alkyl having 1 to 6 carbon atoms and r are integers from 1 to 16. 11. Material according to claim 7, characterized in that the aromatic radical has the formulas

or

corresponds, in which R ⁴ in the case of mono substitution alkyl with 1 to 6 C atoms and the other R ^{4 are} hydrogen, and in the case of di, tri or tetra substitution two R ⁴ alkyl with 1 to 6 C atoms and the others R ^{4 is} a hydrogen atom or alkyl having 1 to 6 C atoms or two in the case of di, tri or tetra substitution vicinal R in the phenyl ring represents trimethylene or tetramethylene and the other R represent a hydrogen atom or alkyl having 1 to 6 C atoms, Y represents 0, S, NH, CO or CH ₂ , R ^{5 represents} a hydrogen atom or alkyl having 1 to 5 C atoms and R ^{6 represents} alkyl with 1 to 5 C atoms, and Z is a direct bond, 0, S, SO, SO ₂ . CO,

NR ⁷ , CONH, NH, R ⁷ SiR ⁸ , R ⁷ OSiOR ⁸ ,

Alkylene having 1 to 6 C-atoms, alkenylene or alkylidene of 2 to 6 carbon atoms, phenylene or Phenyldioxyl is wherein R ⁷ and R ⁸ are independently alkyl having 1 to 6 carbon atoms or phenyl and j is 1 _- 10 stands. 12. Material according to claim 11, characterized in that the aromatic radical

or

is in which Z is a direct bond, 0 and especially CH ₂ and R ^{9 represents} a hydrogen atom, methyl or ethyl. 13. Material according to claim 1, characterized in that the homo- or copolymer is selected from the group of polyimides, polyamides, saturated polyesters, polycarbonates, polyamideimides, polyesterimides, polyesteramides, polysiloxanes, unsaturated polyesters, epoxy resins, the aromatic polyether, the aromatic Polyether ketones, aromatic polyether sulfones, aromatic polyketones, aromatic polythioethers or mixtures of these polymers. 14. Material according to claim 13, characterized in that the polymer is a polyimide with recurring structural elements of the formula I, where q = 0, or a copolyimide of recurring structural elements of the formula I, where q = 0, and recurring structural elements of the formula II

wherein A is a tetravalent organic radical and R ^{10 is} a divalent organic radical. 15. Material according to claim 13, characterized in that the polymer is a polyamide or copolyamide of organic diamines, dicarboxylic acids, ω-aminocarboxylic acids and diamines or dicarboxylic acids with structural elements of the formulas I, in which q = 1 and in which the R and R 'Groups amine groups or carboxyl groups are bound, as well as from mixtures of the monomers. 16. Material according to claim 13, characterized in that the polymer is a polyester or copolyester of organic diols, dicarboxylic acids, hydroxycarboxylic acids and diols or dicarboxylic acids with structural elements of the formula I, in which q = 1 and in which the R- and R'- Groups hydroxyl or carboxyl groups are bound, as well as from mixtures of the monomers. 17. A method for producing a protective layer or a relief image on a support, characterized in that a coated material according to claim 1 is optionally exposed imagewise through a photomask and then optionally the unexposed portions are removed with a developer.